JP6379705B2 - Arylamine polymer, production method thereof and use thereof - Google Patents

Description

  The present invention relates to an arylamine polymer, a method for producing the same, and an application thereof.

  An organic EL (electroluminescence) element usually has a structure in which a plurality of organic thin films are sandwiched between a pair of electrodes, and has recently been used in various applications such as portable displays and lighting fixtures. Low molecular weight compounds are the current mainstream materials used for the organic thin film layer, but the production cost is high because vacuum deposition is generally used to form the organic thin film layer of the low molecular weight compound. There was a problem. For this reason, there is a demand for the development of high-molecular materials that can be applied and formed at low manufacturing costs.

Moreover, in an organic EL element, it is industrially strongly desired to use a phosphorescent material having excellent luminous efficiency. In such phosphorescent organic EL devices, it is generally known that it is necessary to use peripheral materials (a hole transport material and an electron transport material) having a high excited triplet level (T ₁ ).

Examples of the polymer hole injection material, hole transport material, and light-emitting host material include PEDOT-PSS, poly- (N, N′-bis (4-butylphenyl) -N, N′-bis ( Arylamine polymers represented by (phenyl) benzidine) and the like have been proposed (for example, see Patent Documents 1 to 6). However, these conventionally known materials are sufficient in phosphorescent organic EL devices because T ₁ is not high. Performance was not obtained.

JP-A-11-292828 Japanese Patent Laid-Open No. 13-98023 JP 2004-292882 A JP-T-2001-527102 JP-A-56-135448 JP 59-046249 A

  The present invention has been made in view of the above-mentioned background art, and its purpose is to produce an arylamine polymer having a higher excited triplet level than conventionally known ones and excellent in driving voltage and luminous efficiency of an organic electroluminescent device, and production thereof A method and an organic electroluminescent device comprising the method are provided.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found an arylamine polymer in which at least two structures represented by the following general formula (1a) or (1b) are linked repeatedly. The invention has been completed.

  That is, the present invention is an arylamine polymer in which at least two or more structures represented by the following general formula (1a) or (1b) are repeatedly connected (hereinafter referred to as “arylamine polymer (1a) or (1b)” as appropriate). ), A production method and use thereof, and an organic electroluminescent device using the arylamine polymer (1a) or (1b).

(Where
Ar ¹ and Ar ² are divalent aromatic hydrocarbon groups having 6 to 60 carbon atoms (excluding the m-phenylene group) or divalent heteroaromatic groups having 4 to 20 carbon atoms (these substituents are each Independently, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, and a phenyl group having an alkoxy group having 1 to 18 carbon atoms , A halogenated phenyl group, and optionally having one or more substituents selected from the group consisting of a phenyl group having a dialkylamino group consisting of an optionally substituted alkyl group having 1 to 6 carbon atoms). Represent.
Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently 1 selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, and a heteroaromatic group having 4 to 20 carbon atoms. Which may have a substituent of more than one species).
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, carbon The phenyl group which has a dialkylamino group which consists of the phenyl group which has a C1-C18 alkoxy group, or the C1-C6 alkyl group which may differ may be represented.
n represents 0-3.
When n is 2 or 3, Ar ² may be the same or different. )
In addition, it is preferable that the structure represented by the said general formula (1a) or (1b) is respectively what is represented by the following general formula (1a ') or (1b').

(Where
Ar ¹ , Ar ² and Ar ^{2 ′} are each independently a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms (excluding an m-phenylene group) or a divalent heteroaromatic group having 4 to 20 carbon atoms. Group (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, 1 or more types of substitution chosen from the group which consists of a phenyl group which has a dialkylamino group which consists of a phenyl group which has 1-18 alkoxy groups, a halogenated phenyl group, and a C1-C6 alkyl group which may differ. Which may have a group).
Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ^{6 ′} each independently represent an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents) Each independently comprises an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, and a heteroaromatic group having 4 to 20 carbon atoms. Which may have one or more substituents selected from the group).
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, carbon It represents a phenyl group having a phenyl group having an alkoxy group of 1 to 18 or a dialkylamino group composed of an optionally substituted alkyl group having 1 to 6 carbon atoms.
p represents 0-2. k represents 0 or 1; )
In addition, the arylamine polymer in which at least two structures represented by the general formula (1a ′) or (1b ′) are repeatedly connected is hereinafter referred to as “arylamine polymer (1a ′) or (1b ′)” as appropriate. Called.

  The arylamine polymer (1a) or (1b) of the present invention has a high excited triplet level as compared with conventionally known polymer compounds. For this reason, the organic EL device using the arylamine polymer (1a) or (1b) of the present invention is expected to be excellent in luminous efficiency and current efficiency. Therefore, the multibranched arylamine polymer of the present invention can provide a phosphorescent or fluorescent organic EL device having high luminance and low power consumption.

1 represents an FT-IR measurement chart of an arylamine polymer (15) obtained in Example 1. 3 represents an FT-IR measurement chart of the arylamine polymer (16) obtained in Example 2. 3 shows an FT-IR measurement chart of the arylamine polymer (17) obtained in Example 3. 3 shows an FT-IR measurement chart of the arylamine polymer (18) obtained in Example 4. 3 shows an FT-IR measurement chart of the arylamine polymer (19) obtained in Example 5. 3 shows an FT-IR measurement chart of the arylamine polymer (20) obtained in Example 6. 3 shows an FT-IR measurement chart of the arylamine polymer (21) obtained in Example 7. The FT-IR measurement chart of the arylamine polymer (22) obtained in Example 8 is represented. The FT-IR measurement chart of the arylamine polymer (23) obtained in Example 9 is represented.

  The present invention is described in detail below.

  The arylamine polymer (1a) or (1b) of the present invention is one in which at least two structures represented by the above general formula (1a) or (1b) are repeatedly connected.

In the arylamine polymers (1a), (1b), (1a ′), and (1b ′), Ar ¹ , Ar ^2, and Ar ^{2 ′} are each independently divalent aromatic carbonized carbon atoms having 6 to 60 carbon atoms. A hydrogen group (excluding an m-phenylene group) or a divalent heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, 18 alkoxy groups, phenyl groups, phenyl groups having an alkyl group having 1 to 18 carbon atoms, phenyl groups having an alkoxy group having 1 to 18 carbon atoms, halogenated phenyl groups, and different ones having 1 to 6 carbon atoms It may have one or more substituents selected from the group consisting of a phenyl group having a dialkylamino group consisting of a good alkyl group.

  Although it does not specifically limit as a C6-C60 bivalent aromatic hydrocarbon group (however, except m-phenylene group), For example, o-phenylene group, p-phenylene group, biphenylylene group, full An orangeyl group, a naphthalene diyl group, an anthracene diyl group, a pyrene diyl group, a terphenylene group, a phenanthracene diyl group, a perylene diyl group, or a triphenylene diyl group can be exemplified.

  The divalent heteroaromatic group having 4 to 20 carbon atoms is not particularly limited. Pyrimidinediyl group, pyrazinediyl group, quinolinediyl group, isoquinolinediyl group, acridinediyl group, carbazolyl group, benzothiazolinediyl group, quinazolinediyl group, quinoxalinediyl group, 1,6-naphthyridinediyl group, 1,8-naphthyridinediyl group, etc. Can be mentioned.

  Although it does not specifically limit as a C1-C18 alkyl group, For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl Group, n-hexyl group, cyclohexyl group, cyclohexadienyl group, octyl group, trifluoromethyl group, benzyl group, phenethyl group and the like.

  Although it does not specifically limit as a C1-C18 alkoxy group, For example, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy Group, n-hexyloxy group, cyclohexyloxy group, cyclohexadienyloxy group, octyloxy group, tetrahydrofuranyloxy group, trifluoromethoxy group, benzyloxy group, phenethyloxy group and the like.

  Although it does not specifically limit as a phenyl group which has a C1-C18 alkyl group, For example, o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl Group, p-ethylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group and the like.

  Although it does not specifically limit as a phenyl group which has a C1-C18 alkoxy group, For example, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m -Ethoxyphenyl group, p-ethoxyphenyl group, o-tert-butoxyphenyl group, m-tert-butoxyphenyl group, p-tert-butoxyphenyl group and the like can be mentioned.

  Although it does not specifically limit as a halogenated phenyl group, For example, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a chlorophenyl group, a dichlorophenyl group, a trichlorophenyl group etc. are mentioned.

  Although it does not specifically limit as a phenyl group which has a dialkylamino group which consists of a C1-C6 alkyl group which may differ, For example, a dimethylaminophenyl group, a diethylaminophenyl group, a dibutylaminophenyl group, a dihexyl Aminophenyl group, methylethylaminophenyl group, methylbutylaminophenyl group, methylhexylaminophenyl group and the like can be mentioned.

Ar ¹ , Ar ² and Ar ^{2 ′} are each independently an o-phenylene group, a p-phenylene group, a naphthylene group, a fluorenediyl group, a dibenzofuran, in that the hole transport property of the arylamine polymer is excellent. Diyl group or dibenzothiophene diyl group (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, or an alkyl group having 1 to 18 carbon atoms). Selected from the group consisting of a phenyl group having, a phenyl group having a C 1-18 alkoxy group, a halogenated phenyl group, and a phenyl group having a dialkylamino group having a different alkyl group having 1 to 6 carbon atoms It may preferably have one or more substituents.

  Of the above substituents, each independently represents an o-phenylene group, a p-phenylene group, a naphthylene group, or a fluorenediyl group (each independently having an alkyl group having 1 to 18 carbon atoms). Is better).

In (1a) and (1b), when n is 2 or 3, Ar ² may be the same or different substituent in the structure serving as a repeating unit.

In the arylamine polymers (1a), (1b), (1a ′), and (1b ′) of the present invention, Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , and Ar ^{6 ′} each independently represent carbon. An aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, It may have one or more substituents selected from the group consisting of a C6-C60 aromatic hydrocarbon group and a C4-C20 heteroaromatic group.

With respect to the following substituents represented by Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , and Ar ^{6 ′} , the same substituents as those represented by Ar ¹ can be exemplified.
-C1-C18 alkyl group-C1-C18 alkoxy group Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , and Ar ^{6 ′ as} an aromatic hydrocarbon group having 6 to 60 carbon atoms, particularly Although it does not limit, a phenyl group, biphenylyl group, naphthalenyl group, anthracenyl group, pyrenyl group, terphenylenyl group, phenanthracenyl group, perylenyl group, triphenylenyl group etc. are mentioned, for example.

^{Ar 3, Ar 4, Ar 5} , Ar 6, and the hetero-aromatic group having 4 to 20 carbon atoms in Ar ^{6 ',} is not particularly limited, for example, furanyl, benzofuranyl group, a dibenzofuranyl group , Thienylenyl group, benzothienylenyl group, dibenzothienylenyl group, pyridylenyl group, pyrimidinyl group, pyrazinyl group, quinolinyl group, isoquinolinyl group, acridinyl group, benzothiazolyl group, quinazolyl group, quinoxalyl group, 1,6-naphthyridinyl group, Examples thereof include a 1,8-naphthyridinyl group.

  In addition, “selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, and a heteroaromatic group having 4 to 20 carbon atoms. The “substituent” may be bonded to a plurality of aromatic hydrocarbon groups having 6 to 60 carbon atoms or heteroaromatic groups having 4 to 20 carbon atoms as long as the effects of the present invention are not impaired. Among these, “selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, and a heteroaromatic group having 4 to 20 carbon atoms. The number of “substituents” is preferably in the range of 1 to 3, and the types of substituents may be the same or different.

Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , and Ar ^{6 ′} are each independently a phenyl group, a biphenylyl group, a fluorenyl group, a carbazolyl group, a dibenzo group in terms of excellent hole transport properties of the arylamine polymer. It is preferably a thienyl group, a dibenzothienylphenyl group, or an N-dibenzothienylcarbazolyl group (which may each independently have an alkyl group having 1 to 18 carbon atoms as a substituent). .

  Among these, each independently, a phenyl group, 4-methylphenyl group, 4-n-butylphenyl group, dibenzothienyl group, dibenzothienylphenyl group, or N-dibenzothienylcarbazolyl group is more preferable.

In the arylamine polymers (1a), (1b), (1a ′), and (1b ′) of the present invention, Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , and Ar ^{6 ′} are the same, respectively. May be different. However, considering the ease of synthesis, Ar ³ , Ar ⁵ , Ar ⁶ , and Ar ^{6 ′} are preferably the same.

R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, carbon It represents a phenyl group having a phenyl group having an alkoxy group of 1 to 18 or a dialkylamino group composed of an optionally substituted alkyl group having 1 to 6 carbon atoms.

With respect to the following substituents represented by R ¹ and R ² , the same substituents as those represented by Ar ¹ can be exemplified.
-C1-C18 alkyl group-C1-C18 alkoxy group-Phenyl group having a C1-C18 alkyl group-Phenyl group having a C1-C18 alkoxy group-C1-C6 A phenyl group having a dialkylamino group consisting of an alkyl group which may be different from each other, wherein R ¹ and R ² are each independently a hydrogen atom, a methyl group, a tert- A butyl group, a phenyl group, a tolyl group, or a methoxyphenyl group is preferable, and each independently preferably a hydrogen atom, a methyl group, a tert-butyl group, or a phenyl group.

  N in the arylamine polymers (1a) and (1b) of the present invention is preferably 0, 1 or 2 in terms of ease of synthesis of the arylamine polymer, and 0 or 1 in terms of availability of raw materials. It is more preferable.

  P in the arylamine polymers (1a ′) and (1b ′) of the present invention is preferably 0 or 1.

  In addition, the arylamine polymers (1a), (1b), (1a ′), and (1b ′) are terminated with the following general formula (2) from the viewpoint of light emission characteristics and durability as an organic electroluminescence device. It is preferable that it is a substituent represented by these.

(In the formula, Ar ⁷ is an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, A C1-C18 alkoxy group, a phenyl group, a phenyl group having a C1-C18 alkyl group, a phenyl group having a C1-C18 alkoxy group, a halogenated phenyl group, and a C1-C6 It may have one or more substituents selected from the group consisting of phenyl groups having dialkylamino groups that may be different alkyl groups).
The following substituent groups represented by Ar ^7, can be exemplified the same substituents as the substituents shown by Ar ¹ or Ar ^3.
Aromatic hydrocarbon group having 6 to 60 carbon atoms (same as the example shown for Ar ³ )
-Heteroaromatic group having 4 to 20 carbon atoms (same as the example shown for Ar ³ )
- alkyl group having 1 to 18 carbon atoms (exemplified as the same as shown in Ar ¹⁾
- alkoxy group having 1 to 18 carbon atoms (exemplified as the same as shown in Ar ¹⁾
A phenyl group having an alkyl group having 1 to 18 carbon atoms (same as the example shown for Ar ¹ )
A phenyl group having an alkoxy group having 1 to 18 carbon atoms (same as the example shown for Ar ¹ )
-Halogenated phenyl group (same as the example shown for Ar ¹ )
A phenyl group having a dialkylamino group consisting of an alkyl group having 1 to 6 carbon atoms which may be different (same as the example shown for Ar ¹ )
As for Ar ⁷ , each is independently a phenyl group (the phenyl groups are each independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms) in terms of excellent production efficiency of the arylamine polymer. Group, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, a phenyl group having an alkoxy group having 1 to 18 carbon atoms, a halogenated phenyl group, and an optionally substituted alkyl group having 1 to 6 carbon atoms It may preferably have one or more substituents selected from the group consisting of a phenyl group having a dialkylamino group, and each independently represents an o-tolyl group, an m-tolyl group, A p-tolyl group or a phenyl group is more preferable.

  That is, the arylamine polymer (1a) or (1b) is preferably an arylamine polymer represented by the following general formula (3a) or (3b).

(In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , R ¹ , R ² , and n are each independently the same as those in the general formula (1a) or (1b) described above. Ar ⁷ each independently represents the same definition as in the general formula (2), m represents an integer of 2 or more, and when n is 2 or 3, Ar ² is the same. Or different.)

(In the formula, Ar ¹ , Ar ² , Ar ^{2 ′} , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ^{6 ′} , R ¹ , R ² , p and k each independently represent the above-mentioned general formula (The same definition as (1a ′) or (1b ′). Ar ⁷ independently represents the same definition as in the general formula (2). M represents an integer of 2 or more.)
In the general formula (3a), (3b), (3a ′) or (3b ′), Ar ¹ , Ar ² , Ar ^{2 ′} , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ^{6 ′} , Ar ⁷ , R ¹ , R ² , n, p, and k are preferably as described above.

  The arylamine polymer (1a), (1b), (1a ′) or (1b ′) of the present invention is not particularly limited as long as it falls within the above definition, but the luminous efficiency and lifetime of the organic electroluminescent device. It is preferable that it is what is represented in either of the following general formula (4)-(11) at the points of physical properties, such as.

(In the above general formulas (4) to (10) and (51) to (54),
R ¹ and R ² have the same definition as in the general formula (1a) or (1b).
R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{6 ′} each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an aromatic group having 6 to 60 carbon atoms. Represents a hydrocarbon group or a heteroaromatic group having 4 to 20 carbon atoms.
R ⁷ , R ⁸ and R ⁹ each independently have a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, or an alkyl group having 1 to 18 carbon atoms. It represents a phenyl group, a phenyl group having a C1-C18 alkoxy group, a halogenated phenyl group, or a phenyl group having a dialkylamino group consisting of a C1-C6 alkyl group which may be different.
m represents an integer of 2 or more. )
With respect to the following substituents represented by R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{6 ′} , the same substituents as those represented by Ar ¹ can be exemplified.
- an alkyl group having 1 to 8 carbon atoms (exemplified as the same as shown in Ar ¹⁾
- an alkoxy group having 1 to 8 carbon atoms (exemplified as the same as shown in Ar ¹⁾
Aromatic hydrocarbon group having 6 to 60 carbon atoms (same as the example shown for Ar ³ )
-Heteroaromatic group having 4 to 20 carbon atoms (same as the example shown for Ar ³ )
R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{6 ′} are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms in terms of excellent polymer production efficiency. More preferably, each is independently a hydrogen atom, a methyl group, or a butyl group.

About the following substituent in R < ⁷ >, R < ⁸ > and R < ⁹ >, the same substituent as the substituent shown by Ar < ¹ > can be illustrated.
-C1-C8 alkyl group-C1-C8 alkoxy group-Phenyl group having C1-C18 alkyl group-Phenyl group having C1-C18 alkoxy group-Halogenated phenyl group- A phenyl group having a dialkylamino group consisting of an alkyl group having 1 to 6 carbon atoms, and R ⁷ , R ⁸ , and R ⁹ are each independently in terms of excellent production efficiency of an arylamine polymer. , A hydrogen atom or a methyl group is preferable.

  Next, a method for producing the arylamine polymer (1a), (1b), (1a ′) or (1b ′) of the present invention will be described.

  The arylamine polymer (1a), (1b), (1a ′), or (1b ′) of the present invention is not particularly limited, but various arylene halides and arylene amines or It can be synthesized by polymerizing arylene halide and arylenediamine in the presence of a catalyst comprising a trialkylphosphine and / or palladium compound and a base.

(In the reaction formulas 1a to 3b, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , R ¹ , R ² , and n are the same as those in the general formula (1a) or (1b). X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represents a chlorine atom, a bromine atom, or an iodine atom, and m represents an integer of 2 or more.)

(In the reaction formulas 1a ′ to 3b ′, Ar ¹ , Ar ² , Ar ^{2 ′} , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ^{6 ′} , R ¹ , R ² , p, and k are represented by the above general formula ( 1 a ′) or (1 b ′), and X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represents a chlorine atom, a bromine atom or an iodine atom, and m is 2 or more. Represents an integer.)
The compound having the structure represented by the general formula (12a), (12b), (12a ′) or (12b ′) obtained from the polymerization step usually has a secondary amino group or a halogen group at the end, or a secondary amino group. Both groups and halogen groups.

  In the protection step, the compound having the structure represented by the general formula (12a), (12b), (12a ′) or (12b ′) obtained in the polymerization step in the presence of a palladium catalyst and a base and the following general formula It is carried out by a reaction with an aromatic halogen compound represented by (13) or an aromatic amine compound represented by the following general formula (14), or both.

(In the formula, Ar ⁷ has the same definition as Ar ⁷ in the general formula (2). X ⁶ represents a chlorine atom, a bromine atom, or an iodine atom.)

(In the formula, Ar ⁷ each independently has the same definition as Ar ⁷ in the general formula (2).)
Arylamine polymer (1a), (1b), (1a ′) or (1b ′) with the reaction end protected as a product of the protection step, that is, the following general formula (3a), (3b), (3a ′) or An arylamine polymer represented by (3b ′) can be obtained.

(Wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , R ¹ , R ² , and n are each independently the same as defined in General Formula (1) above) Ar ⁷ each independently represents the same definition as in the general formula (2), m represents an integer of 2 or more, and when n is 2 or 3, Ar ² is the same as May be different.)

(In the formula, Ar ¹ , Ar ² , Ar ^{2 ′} , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ^{6 ′} , Ar ⁷ , R ¹ , R ² , p and k are each independently defined above. And Ar ⁷ each independently represents the same definition as in the general formula (2), and m represents an integer of 2 or more.
The protection step may be carried out in one pot following the polymerization step, or the arylamine of the general formula (12a), (12b), (12a ′) or (12b ′) which is a product of the polymerization step. After the polymer is isolated, it may be carried out separately in the presence of a palladium catalyst and a base.

  In the protection step, it is possible to carry out the reaction using the aromatic halogen compound represented by the general formula (13) and the aromatic amine compound represented by the general formula (14) at the same time. In terms of reaction efficiency, the reaction with the aromatic halogen compound and the reaction with the aromatic amine compound are preferably performed separately. In the case of performing the reaction separately, either the reaction using an aromatic halogen compound or the reaction using an aromatic amine compound may be performed first.

  In the protection step, the reaction using the aromatic halogen compound and the reaction using the aromatic amine compound can be carried out continuously in one pot. After one reaction, the reaction product is isolated and separated in a separate batch. The other reaction can also be performed.

  The aromatic halogen compound represented by the general formula (14) is not particularly limited. For example, bromobenzenes which may have a substituent [specifically, bromobenzene, 2-bromotoluene] 3-bromotoluene, 4-bromotoluene, 2-bromo-m-xylene, 2-bromo-p-xylene, 3-bromo-o-xylene, 4-bromo-o-xylene, 4-bromo-m-xylene , 5-bromo-m-xylene, 1-bromo-2-ethylbenzene, 1-bromo-4-ethylbenzene, 1-bromo-4-propylbenzene, 1-bromo-4-n-butylbenzene, 1-bromo-4 -Tert-butylbenzene, 1-bromo-5- (trifluoromethoxy) benzene, 2-bromoanisole, 3-bromoanisole, 4-bromoanisole, 1 Bromonaphthalene, 2-bromonaphthalene, 2-bromobiphenyl, 3-bromobiphenyl, 4-bromobiphenyl, 9-bromoanthracene, 9-bromophenanthrene, N-methyl-3-bromocarbazole, N-ethyl-3- Bromocarbazole, N-propyl-3-bromocarbazole, N-butyl-3-bromocarbazole, 2-bromofluorene, 2-bromo-9,9-dimethylfluorene, 2-bromo-9,9-diethylfluorene, 2- Bromo-9,9-diisopropylfluorene, 2-bromo-9,9-di-n-butylfluorene, 2-bromo-9,9-di-tert-butylfluorene, 2-bromo-9,9-di-sec -Butylfluorene, 2-bromo-9,9-di-n-hexylfluorene, 2-bromo-9,9 Di-n-octylfluorene, 2-bromodibenzothiophene, 2-bromodibenzofuran, etc.], and optionally substituted chlorobenzenes [specifically, chlorobenzene, 2-chlorotoluene, 3-chlorotoluene, 4- Chlorotoluene, 2-chloro-m-xylene, 2-chloro-p-xylene, 3-chloro-o-xylene, 4-chloro-o-xylene, 4-chloro-m-xylene, 5-chloro-m-xylene 1-chloro-2-ethylbenzene, 1-chloro-4-ethylbenzene, 1-chloro-4-propylbenzene, 1-chloro-4-n-butylbenzene, 1-chloro-4-tert-butylbenzene, 1-chlorobenzene Chloro-5- (trifluoromethoxy) benzene, 2-chloroanisole, 3-chloroanisole, 4-chloroanisole, 1- Chloronaphthalene, 2-chloronaphthalene, 2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 9-chloroanthracene, 9-chlorophenanthrene, N-methyl-3-chlorocarbazole, N-ethyl-3- Chlorocarbazole, N-propyl-3-chlorocarbazole, N-butyl-3-chlorocarbazole, 2-chlorofluorene, 2-chloro-9,9-dimethylfluorene, 2-chloro-9,9-diethylfluorene, 2- Chloro-9,9-diisopropylfluorene, 2-chloro-9,9-di-n-butylfluorene, 2-chloro-9,9-di-tert-butylfluorene, 2-chloro-9,9-di-sec -Butyl fluorene, 2-chloro-9,9-di-n-hexyl fluorene, 2-chloro-9,9- -N-octylfluorene, 2-chlorodibenzothiophene, 2-chlorodibenzofuran, etc.] and iodobenzenes which may have a substituent [specifically, iodobenzene, 2-iodotoluene, 3-iodotoluene] 4-iodotoluene, 2-iodo-m-xylene, 2-iodo-p-xylene, 3-iodo-o-xylene, 4-iodo-o-xylene, 4-iodo-m-xylene, 5-iodo- m-xylene, 1-iodo-2-ethylbenzene, 1-iodo-4-ethylbenzene, 1-iodo-4-propylbenzene, 1-iodo-4-n-butylbenzene, 1-iodo-4-tert-butylbenzene 1-iodo-5- (trifluoromethoxy) benzene, 2-iodoanisole, 3-iodoanisole, 4-iodoanisole 1-iodonaphthalene, 2-iodonaphthalene, 2-iodobiphenyl, 3-iodobiphenyl, 4-iodobiphenyl, 9-iodoanthracene, 9-iodophenanthrene, N-methyl-3-iodocarbazole, N-ethyl- 3-iodocarbazole, N-propyl-3-iodocarbazole, N-butyl-3-iodocarbazole, 2-iodofluorene, 2-iodo-9,9-dimethylfluorene, 2-iodo-9,9-diethylfluorene, 2-iodo-9,9-diisopropylfluorene, 2-iodo-9,9-di-n-butylfluorene, 2-iodo-9,9-di-tert-butylfluorene, 2-iodo-9,9-di -Sec-butylfluorene, 2-iodo-9,9-di-n-hexylfluorene, 2-iodo-9, 9-di-n-octylfluorene, 2-iododibenzothiophene, 2-iododibenzofuran, etc.].

  The aromatic amine compound represented by the general formula (14) is not particularly limited, and examples thereof include diphenylamine, di-p-tolylamine, N-phenyl-1-naphthylamine, and N-phenyl-2-naphthylamine. Etc.

  The polymerization step and the protection step are both carried out in the presence of a palladium catalyst and a base, and the reaction conditions are not particularly limited, but the following may be used. it can. The palladium catalyst usually comprises a palladium compound and a ligand.

  Although it does not specifically limit as a palladium compound which is a structural component of a palladium catalyst, For example, tetravalent palladium compounds [Specifically, sodium hexachloro palladium (IV) acid tetrahydrate, hexachloro palladium (IV Potassium diacid), divalent palladium compounds (for example, palladium chloride (II), palladium bromide (II), palladium acetate (II), palladium (II) acetylacetonate, dichlorobis (benzonitrile) palladium (II ), Dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium (II) trifluoroa Tate etc.], and zero-valent palladium compounds [specifically, tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, tetrakis (triphenylphosphine) palladium (0) etc.].

  The ligand that is a constituent component of the palladium catalyst is not particularly limited, but may be any ligand that can coordinate to palladium, such as trialkylphosphines, arylphosphines, carbene-based ligands, and the like. Is mentioned.

  Although it does not specifically limit as trialkyl phosphine, For example, a triethyl phosphine, a tricyclohexyl phosphine, a triisopropyl phosphine, a tri-n-butyl phosphine, a triisobutyl phosphine, a tri-sec-butyl phosphine, a tri-tert- And butylphosphine. Of these, tri-tert-butylphosphine is preferably used because of its particularly high reaction activity as a catalyst.

  The aryl phosphines are not particularly limited, and examples thereof include triphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, and 2,2′-bis. (Diphenylphosphino) -1,1′-binaphthyl (BINAP), trimesitylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinoferrocene and the like.

  Examples of the carbene-based ligand include 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene hydrochloride.

  The amount of the ligand used in the palladium catalyst is not particularly limited, but it may be used usually in the range of 0.01 to 10000 times mol of 1 mol of palladium atom in the palladium compound, and expensive trialkyl. Since phosphines, arylphosphines, and carbene-based ligands are used, the range of 0.1 to 10 moles per mole of palladium atom in the palladium compound is preferable.

  Although the usage-amount of the palladium catalyst in a superposition | polymerization process is not specifically limited, For example, Reaction formula (1a), (1b), (1a ') or (1b'), Reaction formula (2a), (2b) In the polymerization step of (2a ′) or (2b ′) and reaction formula (3a), (3b), (3a ′) or (3b ′), it is usually 0 in terms of palladium atom with respect to 1 mol of the halogen atom of the raw material. The range is preferably 0.00000000 to 0.20 moles. Of these, from the viewpoint of catalytic activity and the use of an expensive palladium compound, it is usually more preferably in the range of 0.00001 to 0.05 times mole.

  Although the usage-amount of the palladium catalyst in a protection process is not specifically limited, The aromatic halogen compound represented by General formula (13), or General formula (12a), (12b), (12a ') or It is preferably in the range of usually 0.0000001 to 0.20 times mol in terms of palladium atom with respect to 1 mol of halogen atom of the polymer represented by (12b ′). Of these, from the viewpoint of catalytic activity and the use of expensive palladium compounds, it is usually more preferably in the range of 0.00001 to 0.10 times mole.

  The method for adding the palladium catalyst in the polymerization step and the protection step is not particularly limited, but a palladium compound, a ligand, and other components may be added individually to the reaction system in the polymerization step or the protection step. The catalyst components may be added in advance and mixed in the form of a palladium complex.

  Although it does not specifically limit as a base used for a superposition | polymerization process and a protection process, For example, inorganic bases, such as a hydroxide of alkali metals (specifically sodium, potassium, etc.), carbonate, an alkoxide, or Organic bases such as tertiary amines can be mentioned. Of these, preferred are alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide, and the like. It can be added as it is to the system, or it can be prepared in situ by subjecting an alkali metal, alkali metal hydride or alkali metal hydroxide and alcohol to the reaction system. More preferred is a method in which an alkali metal tertiary alkoxide such as lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide or the like is added to the reaction system as it is.

  The amount of base used in the polymerization step is not particularly limited, but is not particularly limited. For example, it is represented by the reaction formula (1a), (1b), (1a ′) or (1b ′). Reaction of arylene halide and arylamine, reaction of arylene halide represented by reaction formula (2a), (2b), (2a ′) or (2b ′), arylene amine, reaction formula (3a), In the reaction between the arylene halide represented by (3b), (3a ′) or (3b ′) and the arylene diamine, it is selected from a range of 1 to 1000 moles per mole of the halogen atoms of the raw arylene halide. It is. Among these, the range of 1 to 20 times mol is more preferable in consideration of the post-treatment operation after completion of the reaction.

  The amount of the base used in the protection step is not particularly limited, but is usually in the range of 1 to 1000 times mol with respect to 1 mol of the halogen atom of the aromatic halogen compound represented by the general formula (13), preferably Is in the range of 1 to 20 times mol, or in the range of 1 to 100000 times mol, preferably 1 to 1000 times the mol of the halogen atom of the polymer having the structure represented by the general formula (12a) or (12b). Selected from a range of moles.

  Both the polymerization step and the protection step are usually preferably carried out in the presence of an inert solvent. The solvent used is not particularly limited as long as it does not significantly inhibit this reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane. A solvent, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphotriamide, etc. can be mentioned. Of these, aromatic hydrocarbon solvents such as benzene, toluene and xylene are preferred.

  The polymerization step and the protection step are preferably carried out under normal pressure and in an inert gas atmosphere such as nitrogen or argon, but can be carried out even under pressurized conditions.

  The reaction temperature in the polymerization step and the protection step is not particularly limited as long as the reaction proceeds at an economically acceptable rate, but is usually 20 to 300 ° C., preferably 50 to 200 ° C. Preferably it is the range of 100-150 degreeC.

  The reaction time in the polymerization step and the protection step is not particularly limited because it is not constant depending on the arylamine polymer to be produced, the palladium catalyst, the reaction temperature, etc. In many cases, the reaction time is from a range of several minutes to 72 hours. Just choose. Preferably it is less than 24 hours.

  The arylamine polymer (1a), (1b), (1a ′) or (1b ′) produced by the polymerization step and the protection step is separated from unreacted low molecular weight compounds by reprecipitation and purified. Is preferred. Moreover, it is preferable to perform adsorption treatment with silica gel, activated alumina or the like in order to remove impurities such as a palladium catalyst.

  The arylamine polymer (1a), (1b), (1a ′) or (1b ′) of the present invention has high conductivity in electronic devices such as field effect transistors, optical functional devices, dye-sensitized solar cells, and organic EL devices. Used as molecular material. In particular, it is extremely useful as a hole transport material, a light emitting material and a buffer material of an organic EL device.

  The element structure is not particularly limited as long as the organic EL element of the present invention includes an organic layer containing the arylamine polymer (1a), (1b), (1a ′) or (1b ′) of the present invention.

  Since the arylamine polymer (1a), (1b), (1a ′) or (1b ′) of the present invention is excellent in solubility, for example, a solution, a mixed solution, or a melt of these materials is used. The element can be easily produced by a conventionally known coating method such as a spin coating method, a casting method, a dipping method, a bar coating method, or a roll coating method. It can also be easily produced by an inkjet method, a Langmuir Blodget method, or the like.

  The basic structure of the organic EL device that can obtain the effects of the present invention includes a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode.

  The anode and cathode of the organic EL element are connected to a power source through an electrical conductor. The organic EL element operates by applying a potential between the anode and the cathode.

  Holes are injected into the organic EL element from the anode, and electrons are injected into the organic EL element at the cathode.

  The organic EL element is typically placed on a substrate, and the anode or cathode can be in contact with the substrate. The electrode in contact with the substrate is called the lower electrode for convenience. Generally, the lower electrode is an anode, but the organic EL element of the present invention is not limited to such a form.

  The substrate may be light transmissive or opaque depending on the intended emission direction. The light transmission characteristics can be confirmed by electroluminescence emission through the substrate. Generally, transparent glass or plastic is used as the substrate in such a case. The substrate may be a composite structure including multiple material layers.

  When the electroluminescent emission is confirmed through the anode, the anode is formed by passing or substantially passing through the emission.

  The general transparent anode (anode) material used in the present invention is not particularly limited, and examples thereof include indium-tin oxide (ITO), indium-zinc oxide (IZO), and tin oxide. . Other metal oxides such as aluminum or indium doped tin oxide, magnesium-indium oxide, or nickel-tungsten oxide can also be used. In addition to these oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, or metal sulfides such as zinc sulfide can be used as the anode.

  The anode can be modified with plasma deposited fluorocarbon. If electroluminescence emission is confirmed only through the cathode, the transmission properties of the anode are not critical and any conductive material that is transparent, opaque or reflective can be used. Examples of conductors for this application include gold, iridium, molybdenum, palladium, platinum and the like.

  A hole injection layer can be provided between the anode and the hole transport layer. The hole injection material serves to improve the subsequent film-forming properties of the organic layer and to facilitate injection of holes into the hole transport layer.

  Examples of materials suitable for use in the hole injection layer include polythiophene derivatives, polyaniline derivatives, polypyrrole derivatives, preferably examples of materials suitable for use in the hole injection layer, preferably Examples include polythiophene derivatives.

  For the hole transport layer of the organic EL device, the arylamine polymer of the present application is preferably used. In addition to the arylamine polymer of the present application, the hole transport layer may contain one or more hole transport compounds such as aromatic tertiary amines. An aromatic tertiary amine means a compound containing one or more trivalent nitrogen atoms, and these trivalent nitrogen atoms are bonded only to carbon atoms, and one of these carbon atoms One or more form an aromatic ring. Specifically, aromatic tertiary amines include arylamines, monoarylamines, diarylamines, triarylamines, or polymeric arylamines. More specifically, for example, poly (N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline, NPD (N, N′-bis (naphthalen-1-yl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine), α- NPD (N, N′-di (1-naphthyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine), TPBi (1,3,5-tris (1-phenyl-) 1H-benzimidazol-2-yl) benzene), or TPD (N, N′-bis (3-methylphenyl) -N, N′-diphenyl-1,1′-biphenyl-4,4 - diamine), and the like.

  Dipyrazino [2,3-f: 2 ′, 3′-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile as a charge generation layer between the hole injection layer and the hole transport layer A layer containing (HAT-CN) may be provided.

  The light emitting layer of the organic EL element contains a phosphorescent material or a fluorescent material, and emits light as a result of recombination of electron / hole pairs in this region.

  The emissive layer may consist of a single material that includes both small molecules and polymers, but more commonly consists of a host material doped with a guest compound, where the emission occurs primarily from the dopant, Can have a color.

  Examples of the host material for the light emitting layer include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, or an anthranyl group. For example, DPVBi (4,4′-bis (2,2-diphenylvinyl) -1,1′-biphenyl), BCzVBi (4,4′-bis (9-ethyl-3-carbazovinylene) 1,1′-biphenyl ), TBADN (2-tert-butyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4′-bis (carbazole-9) -Yl) biphenyl), CDBP (4,4′-bis (carbazol-9-yl) -2,2′-dimethylbiphenyl), 9,10-bis (biphenyl) anthracene and the like.

  The host material in the light emitting layer may be an electron transport material as defined below, a hole transport material as defined above, another material that supports hole / electron recombination (support), or a combination of these materials. Good.

  Examples of fluorescent dopants include anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compound, thiopyran compound, polymethine compound, pyrylium or thiapyrylium compound, fluorene derivative, perifuranthene derivative, indenoperylene derivative, Examples thereof include bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, and carbostyryl compounds.

  As an example of the phosphorescent dopant, an organometallic complex of a transition metal such as iridium, platinum, palladium, or osmium can be given.

Examples of dopants include Alq ₃ (tris (8-hydroxyquinoline) aluminum)), DPAVBi (4,4′-bis [4- (di-para-tolylamino) styryl] biphenyl), perylene, Ir (PPy) ₃ ( Examples include tris (2-phenylpyridine) iridium (III), FlrPic (bis (3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) iridium (III)), and the like.

  Examples of the electron transporting material include alkali metal complexes, alkaline earth metal complexes, and earth metal complexes. Examples of the alkali metal complex, alkaline earth metal complex, or earth metal complex include 8-hydroxyquinolinate lithium (Liq), bis (8-hydroxyquinolinato) zinc, and bis (8-hydroxyquinolinate). Copper, bis (8-hydroxyquinolinato) manganese, tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, Bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolate) gallium, bis (2-methyl-8-quinolinate) 1-naphthyl Trat aluminum, bis (2-methyl-8-quinolinato) -2-naphthoquinone Trad gallium, and the like.

  A hole blocking layer may be provided between the light emitting layer and the electron transport layer for the purpose of improving carrier balance. Desirable compounds for the hole element layer are BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis (2 -Methyl-8-quinolinolato) -4- (phenylphenolato) aluminum) or bis (10-hydroxybenzo [h] quinolinato) beryllium).

  In the organic EL device of the present invention, an electron injection layer may be provided for the purpose of improving electron injection properties and improving device characteristics (for example, light emission efficiency, constant voltage driving, or high durability).

Preferred compounds for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, etc. Is mentioned. In addition, the above-described metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO ₂ , AlO, SiN, SiON, AlON, Various oxides such as GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, and C, and inorganic compounds such as nitride and oxynitride can also be used.

If light emission is confirmed only through the anode, the cathode used in the present invention can be formed from any conductive material. Desirable cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, indium , Lithium / aluminum mixtures, rare earth metals and the like.

  Examples of the present invention are shown below, but the present invention is not construed as being limited to these examples.

  Polymer molecular weight: THF GPC [HLC-8220 (manufactured by Tosoh Corporation). The columns were TSKgel-SuperH4000, TSKgel-SuperH3000, and TSKgel-SuperH2000 (all manufactured by Tosoh Corporation). ], The molecular weight of the synthesized polymer was measured. The molecular weight is shown in terms of standard polystyrene.

  Glass transition temperature: Measured using DSC200F3 (manufactured by Netch).

  HOMO level: Measured using an atmospheric photoelectron spectrometer apparatus AC-3 (manufactured by Riken Keiki Co., Ltd.).

  LUMO level: The energy gap (Eg) was calculated from the absorption edge of the UV-vis absorption spectrum and subtracted from HOMO.

  Elemental analysis: Analysis was performed using a fully automatic elemental analyzer 2400II (Perkin Elmer).

Example 1
Into a 1 L four-necked round bottom flask equipped with a condenser and a thermometer, at room temperature, 36.8 g (192 mmol) of p-bromochlorobenzene, 10.0 g (93.3 mmol) of p-toluidine, sodium tert-butoxide 46. 2 g (481 mmol) and 440 g of o-xylene were charged. To this mixed solution, a solution of 0.84 g (3.73 mmol) of palladium (II) acetate and 2.27 g (11.2 mmol) of tri-tert-butylphosphine prepared in advance in a nitrogen atmosphere in an o-xylene (15.0 g) solution. Was added. Thereafter, the temperature was raised to 100 ° C. in a nitrogen atmosphere, and the mixture was aged for 20 hours while heating and stirring at 100 ° C. Thereafter, 41.2 g of p-toluidine was added and reacted at 120 ° C. for 20 hours. Next, when the mixture was allowed to cool to 80 ° C., 100 g of pure water was added to the reaction solution, and then allowed to cool to room temperature with stirring. Subsequently, extraction operation was performed by adding 200 mL of toluene. The extracted organic layer was passed through silica gel column chromatography, and then toluene was removed by distillation under reduced pressure to obtain a residue. The product was purified by a recrystallization operation using toluene as a solvent to obtain 55.3 g of compound (15a).

  In a 100 mL four-necked round bottom flask equipped with a condenser and a thermometer, 0.51 g (1.08 mmol) of compound (15a) and 0.43 g of 3,6-dibromo-9-phenylcarbazole at room temperature under a nitrogen atmosphere (1.08 mmol), 0.42 g (4.34 mmol) of sodium-tert-butoxide and 6.2 g of o-xylene were mixed. Nitrogen was allowed to flow through the reaction vessel for about 20 minutes, and then 9.9 mg (10.8 μmol) of tris (dibenzylideneacetone) dipalladium and tri-tert-butylphosphine previously prepared in a nitrogen atmosphere were added to this mixed solution. An additional 5 mg (86.7 μmol) of o-xylene (1.5 mL) solution was added. Subsequently, it stirred at the temperature of 120 degreeC for 15 hours. Subsequently, 85.1 mg (0.54 mmol) of bromobenzene was added, and the mixture was further stirred at 120 ° C. for 3 hours. Thereafter, 0.18 g (1.08 mmol) of diphenylamine was further added, and the mixture was further stirred at 120 ° C. for 3 hours. The reaction mixture was then cooled to about 60 ° C., after which 2 g of water was added to the reactor and stirred for 1 hour. It was then slowly added to a stirred solution of 90% aqueous acetone (100 mL). The precipitated solid was collected by filtration, washed in the order of acetone, water, and acetone, and then dried under reduced pressure to obtain 0.63 g of a light yellow powdery arylamine polymer (15) (82%).

The obtained arylamine polymer (15) had a weight average molecular weight of 55,000 and a number average molecular weight of 7,000 (dispersity of 7.9) in terms of polystyrene.

  The glass transition temperature was 270 ° C.

  The HOMO level was 5.02 eV, and the LUMO level was 1.83 eV.

  Table 1 shows the results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 2
A 1 L four-necked round bottom flask equipped with a condenser and a thermometer was charged with 19.3 g (57.2 mmol) of N, N-diphenyl-N-2-dibenzothienylamine, N, N-dimethylformamide (hereinafter referred to as “room temperature”) at room temperature. , Abbreviated as DMF), and 400 g were charged and cooled to 0 ° C. A solution of 21.0 g (118 mmol) of N-bromosuccinimide in DMF (150 g) was slowly added dropwise to the mixture over 30 minutes with stirring. Subsequently, after stirring at 0 degreeC for 1 hour, it heated up gradually to room temperature, and also stirred for 2 hours. Subsequently, 200 g of 10% sodium thiosulfate aqueous solution was added and stirred for 30 minutes, and then 500 mL of toluene was added to perform extraction operation. The extracted organic layer was washed with 300 mL of pure water three times, passed through silica gel column chromatography, and then toluene was removed by distillation under reduced pressure to obtain a residue. Purification by recrystallization using toluene as a solvent gave 20.1 g of compound (16a).

  In a 300 mL four-necked round bottom flask equipped with a condenser and a thermometer, at room temperature, 10.0 g (19.6 mmol) of compound (16a), 6.31 g (58.9 mmol) of p-toluidine, sodium-tert-butoxide 4.72 g (49.1 mmol) and 100 g of o-xylene were charged. To this mixed solution, a solution of 0.18 g (0.79 mmol) of palladium (II) acetate and 0.48 g (49.1 mmol) of tri-tert-butylphosphine prepared in advance in a nitrogen atmosphere in an o-xylene (2.0 g) solution. Was added. Thereafter, the temperature was raised to 100 ° C. in a nitrogen atmosphere, and the mixture was aged for 5 hours with heating and stirring at 120 ° C. Next, when the mixture was allowed to cool to 80 ° C., 100 g of pure water was added to the reaction solution, and then allowed to cool to room temperature with stirring. The obtained reaction mixture was extracted by adding 100 mL of toluene. The organic layer was passed through silica gel column chromatography, and then toluene was removed by distillation under reduced pressure to obtain a residue. The product was purified by recrystallization using toluene as a solvent to obtain 7.81 g of compound (16b).

  The same operation as in Example 1 was carried out except that 0.61 g (1.08 mmol) of the compound (16b) was used instead of the compound (15a) to obtain 0.67 g of the compound (16).

  The obtained arylamine polymer (16) had a weight average molecular weight of 26,000 and a number average molecular weight of 5,800 (dispersity of 4.5) in terms of polystyrene.

  The glass transition temperature was 270 ° C.

  The HOMO level was 5.04 eV and the LUMO level was 1.84 eV.

  The measurement results of elemental analysis are shown in Table 2.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 3
To a 500 mL four-necked round bottom flask equipped with a condenser and a thermometer, at room temperature, 12.7 g (76.0 mmol) of carbazole, 20.0 g (76.0 mmol) of 2-bromodibenzothiophene, 21.0 g of potassium carbonate ( 152 mmol), 0.60 g (2.28 mmol) of 18-crown ether and 160 g of o-xylene were charged. To this mixed solution, a solution of 0.51 g (2.28 mmol) of palladium (II) acetate and 1.85 g (9.12 mmol) of tri-tert-butylphosphine prepared in advance in a nitrogen atmosphere in an o-xylene (10.0 g) solution. Was added. Thereafter, the temperature was raised to 130 ° C. in a nitrogen atmosphere, and the mixture was aged for 20 hours while heating and stirring at 100 ° C. Next, when the mixture was allowed to cool to 80 ° C., 100 g of pure water was added to the reaction solution, and then allowed to cool to room temperature with stirring. Extraction operation was performed by adding 100 mL of toluene to the obtained reaction mixture. The extracted organic layer was passed through silica gel column chromatography, and then toluene was removed by distillation under reduced pressure to obtain a residue. Purification by recrystallization using toluene and hexane as solvents gave 20.0 g of compound (17a).

  The same operation as in Example 2 was carried out except that 20.1 g (57.2 mmol) of compound (17a) was used instead of N, N-diphenyl-2-dibenzothienylamine to obtain 23.8 g of compound (17b). It was.

  The same operation as in Example 1 was carried out except that 0.55 g (1.08 mmol) of compound (17b) was used instead of 3,6-dibromo-9-phenylcarbazole to obtain 0.70 g of compound (17). .

  The obtained arylamine polymer (17) had a weight average molecular weight of 33,000 and a number average molecular weight of 6,000 (dispersity of 5.5) in terms of polystyrene.

  The glass transition temperature was 273 ° C.

  The HOMO level was 5.05 eV and the LUMO level was 1.86 eV.

  Table 3 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 4
In a 500 mL four-necked round bottom flask equipped with a condenser and a thermometer, 10.0 g (42.4 mmol) of p-dibromobenzene, 15.8 g (106 mmol) of p-butylaniline, sodium-tert-butoxide 9 at room temperature. 80 g (102 mmol) and 120 g of o-xylene were charged.

  To this mixed solution, a solution of 0.19 g (0.85 mmol) of palladium (II) acetate and 0.69 g (3.40 mmol) of tri-tert-butylphosphine prepared in advance in a nitrogen atmosphere in an o-xylene (2.75 g) solution. Was added. Thereafter, the mixture was heated and stirred at 120 ° C. for 4 hours under a nitrogen atmosphere.

  Next, when the temperature was lowered to 80 ° C. or less by cooling, 100 g of pure water was added to the reaction solution, and then allowed to cool to room temperature with stirring. To the resulting reaction mixture, 200 mL of toluene and 50 mL of tetrahydrofuran were added for extraction. The extracted organic layer was passed through silica gel column chromatography, and then toluene was removed by distillation under reduced pressure to obtain a residue. The product was purified by recrystallization using toluene as a solvent to obtain 10.5 g of compound (18a).

  The same operation as in Example 1 was carried out except that 0.40 g (1.08 mmol) of the compound (18a) was used instead of the compound (15a) to obtain 0.52 g of the compound (18).

The obtained arylamine polymer (18) had a weight average molecular weight of 24,000 and a number average molecular weight of 5,100 (dispersion degree 4.7) in terms of polystyrene.

  The glass transition temperature was 209 ° C.

  The HOMO level was 5.05 eV, and the LUMO level was 1.75 eV.

  Table 4 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 5
The same operation as in Example 4 was carried out except that 0.55 g (1.08 mmol) of compound (17b) was used instead of 3,6-dibromo-9-phenylcarbazole to obtain 0.70 g of compound (19). .

The obtained arylamine polymer (19) had a weight average molecular weight of 25,000 and a number average molecular weight of 4,600 (dispersion degree 5.4) in terms of polystyrene.

  The glass transition temperature was 214 ° C.

The HOMO level was 5.06 eV and the LUMO level was 1.77 eV.
Table 5 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 6
To a 200 mL four-necked round bottom flask equipped with a condenser and a thermometer, 7.00 g (15.3 mmol) of 3,6-dibromo-9- (4-butylphenyl) carbazole and p-butylaniline at room temperature. 85 g (45.9 mmol), sodium tert-butoxide 3.53 g (36.7 mmol) and o-xylene 85 g were charged. In this mixed solution, a solution of 68.7 mg (0.31 mmol) of palladium (II) acetate and 0.186 g (0.92 mmol) of tri-tert-butylphosphine prepared in advance in a nitrogen atmosphere in an o-xylene (5.0 g) solution. Was added. Thereafter, the temperature was raised to 130 ° C. in a nitrogen atmosphere, and the mixture was aged for 16 hours while heating and stirring at 130 ° C. Next, when the mixture was allowed to cool to 80 ° C., 100 g of pure water was added to the reaction solution, and then allowed to cool to room temperature with stirring. Subsequently, extraction operation was performed by adding 50 mL of toluene. The extracted organic layer was passed through silica gel column chromatography, and then toluene was removed by distillation under reduced pressure to obtain a residue. Purification by recrystallization using toluene as a solvent gave 4.73 g of compound (20a).

  A 50 mL four-necked round bottom flask equipped with a condenser and a thermometer was charged with 1.09 g (1.84 mmol) of compound (20a) and 0.60 g (1.84 mmol) of 2,8-dibromodibenzofuran at room temperature under a nitrogen atmosphere. ), 0.71 g (7.36 mmol) of sodium-tert-butoxide and 25.0 g of o-xylene were mixed. After flowing nitrogen through the reaction vessel for about 20 minutes, 16.9 mg (18.4 μmol) of tris (dibenzylideneacetone) dipalladium previously prepared under a nitrogen atmosphere and tri-tert-butylphosphine in this mixed solution A solution of 3 mg (110 μmol) of o-xylene (3.0 mL) was added. Subsequently, it stirred at the temperature of 120 degreeC for 17 hours. Next, 0.17 g (1.10 mmol) of bromobenzene was added, and the mixture was further stirred at 120 ° C. for 3 hours. Thereafter, 0.37 g (2.21 mmol) of diphenylamine was further added, and the mixture was further stirred at 120 ° C. for 3 hours. The reaction mixture was then cooled to about 60 ° C., after which 3 g of water was added to the reactor and stirred for 1 hour. It was then slowly added to a stirred solution of 90% aqueous acetone (300 mL). The precipitated solid was collected by filtration, washed in the order of acetone, water and acetone, and then dried under reduced pressure to obtain 0.55 g of a light yellow powdery arylamine polymer (20) (39%).

The obtained arylamine polymer (20) had a weight average molecular weight of 11,000 and a number average molecular weight of 3,900 (dispersity 2.8) in terms of polystyrene.

  The glass transition temperature was 205 ° C.

  The HOMO level was 5.21 eV, and the LUMO level was 2.43 eV.

  Table 6 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 7
The same operation as in Example 6, except that 0.63 g (1.84 mmol) of 2,8-dibromodibenzothiophene was used instead of 2,8-dibromodibenzofuran, to obtain 0.70 g of compound (21).

The obtained arylamine polymer (21) had a weight average molecular weight of 175,000 and a number average molecular weight of 22,000 (dispersity of 8.0) in terms of polystyrene.

  The glass transition temperature was 226 ° C.

  The HOMO level was 5.13 eV and the LUMO level was 2.36 eV.

  Table 7 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 8
In a 100 mL four-necked round bottom flask equipped with a condenser and a thermometer, 1.00 g (2.49 mmol) of 3,6-dibromo-9-phenylcarbazole and 2.79 g (7.48 mmol) of compound (18a) at room temperature. ), 0.60 g (6.23 mmol) of sodium-tert-butoxide and 38 g of o-xylene. To this mixed solution, a solution of 22.4 mg (0.10 mmol) of palladium (II) acetate and 60.5 mg (0.30 mmol) of tri-tert-butylphosphine prepared in advance in a nitrogen atmosphere in an o-xylene (3.0 g) solution. Was added. Thereafter, the temperature was raised to 130 ° C. in a nitrogen atmosphere, and the mixture was aged for 6 hours while heating and stirring at 130 ° C. Next, when the mixture was allowed to cool to 80 ° C., 50 g of pure water was added to the reaction solution, and then allowed to cool to room temperature with stirring. Subsequently, extraction operation was performed by adding 20 mL of toluene. The extracted organic layer was passed through silica gel column chromatography, and then toluene was removed by distillation under reduced pressure to obtain a residue. The product was purified by recrystallization using toluene as a solvent to obtain 0.89 g of compound (22a).

  In a 50 mL four-necked round bottom flask equipped with a condenser and a thermometer, 0.86 g (0.87 mmol) of compound (22a) and 0.29 g (0.87 mmol) of 2,8-dibromodibenzofuran at room temperature under a nitrogen atmosphere. ), 0.34 g (3.50 mmol) of sodium-tert-butoxide and 18.1 g of o-xylene were mixed. After flowing nitrogen through the reaction vessel for about 20 minutes, 8.0 mg (8.7 μmol) of tris (dibenzylideneacetone) dipalladium prepared in advance in a nitrogen atmosphere and tri-tert-butylphosphine in this mixed solution were used. An additional 6 mg (520 μmol) of o-xylene (2.0 mL) solution was added. Subsequently, it stirred at the temperature of 120 degreeC for 4 hours. Subsequently, 82.4 mg (0.52 mmol) of bromobenzene was added, and the mixture was further stirred at 120 ° C. for 3 hours. Thereafter, 0.18 g (1.05 mmol) of diphenylamine was further added, and the mixture was further stirred at 120 ° C. for 14 hours. The reaction mixture was then cooled to about 60 ° C., after which 2 g of water was added to the reactor and stirred for 1 hour. It was then slowly added to a stirred solution of 90% aqueous acetone (200 mL). The precipitated solid was collected by filtration, washed in the order of acetone, water and acetone, and then dried under reduced pressure to obtain 0.38 g of a pale yellow powdery arylamine polymer (22) (38%).

The obtained arylamine polymer (22) had a weight average molecular weight of 26,000 and a number average molecular weight of 12,000 (dispersity of 2.2) in terms of polystyrene.

  The glass transition temperature was 195 ° C.

  The HOMO level was 5.10 eV, and the LUMO level was 2.19 eV.

  Table 8 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 9
To a 50 mL four-necked round bottom flask equipped with a condenser and a thermometer, 1.30 g of 3,6-bis (4-butylphenylamino) -9- (4-butylphenyl) carbazole at room temperature under a nitrogen atmosphere ( 2.84 mmol), 0.42 g (2.84 mmol) of 4-butylaniline, 1.09 g (11.4 mmol) of sodium-tert-butoxide and 15.2 g of o-xylene were mixed. After allowing nitrogen to flow for about 20 minutes inside the reaction vessel, 26.0 mg (28.4 μmol) of tris (dibenzylideneacetone) dipalladium prepared in advance in a nitrogen atmosphere and tri-tert-butylphosphine 34. An additional 5 mg (0.17 mmol) of o-xylene (3.0 mL) solution was added. Subsequently, it stirred at the temperature of 120 degreeC for 18 hours. Subsequently, 0.27 g (1.71 mmol) of bromobenzene was added, and the mixture was further stirred at 120 ° C. for 3 hours. Thereafter, 0.58 g (3.41 mmol) of diphenylamine was further added, and the mixture was further stirred at 120 ° C. for 3 hours. The reaction mixture was then cooled to about 60 ° C., after which 3 g of water was added to the reactor and stirred for 1 hour. It was then slowly added to a stirred solution of 90% aqueous acetone (200 mL). The precipitated solid was collected by filtration, washed in the order of acetone, water, and acetone, and then dried under reduced pressure to obtain 0.58 g (46%) of a pale yellow powdery arylamine polymer (23).

The obtained arylamine polymer (23) had a weight average molecular weight of 37,000 and a number average molecular weight of 10,000 (dispersion degree 3.7) in terms of polystyrene.

  The glass transition temperature was not detected up to 300 ° C.

  The HOMO level was 4.98 eV, and the LUMO level was 2.27 eV.

  Table 9 shows the results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 10 Measurement of Triplet Level of Arylamine Polymer (15) 1 mg of arylamine polymer (15) and 1 mL of 2-methyltetrahydrofuran were mixed well in a sample tube to prepare a uniform solution. The solution was degassed by bubbling with nitrogen gas for 10 minutes, and then the sample tube was sealed and the phosphorescence spectrum was measured. The triplet level of the arylamine polymer (15) calculated from the obtained phosphorescence spectrum was 2.50 eV.

Example 11 Measurement of Triplet Level of Arylamine Polymer (16) The same operation as in Example 10 was performed except that the arylamine polymer (16) was used instead of the arylamine polymer (15) in Example 10. The phosphorescence spectrum was measured. The triplet level of the arylamine polymer (16) calculated from the obtained phosphorescence spectrum was 2.51 eV.

Example 12 Measurement of Triplet Level of Arylamine Polymer (17) The same operation as in Example 10 was performed except that the arylamine polymer (17) was used instead of the arylamine polymer (15) in Example 10. The phosphorescence spectrum was measured. The triplet level of the arylamine polymer (17) calculated from the obtained phosphorescence spectrum was 2.50 eV.

Example 13 Measurement of Triplet Level of Arylamine Polymer (18) The same operation as in Example 10 was performed except that the arylamine polymer (18) was used instead of the arylamine polymer (15) in Example 10. The phosphorescence spectrum was measured. The triplet level of the arylamine polymer (18) calculated from the obtained phosphorescence spectrum was 2.50 eV.

Example 14 Measurement of Triplet Level of Arylamine Polymer (19) The same operation as in Example 10 was performed except that the arylamine polymer (19) was used instead of the arylamine polymer (15) in Example 10. The phosphorescence spectrum was measured. The triplet level of the arylamine polymer (19) calculated from the obtained phosphorescence spectrum was 2.51 eV.

Example 15 Measurement of Triplet Level of Arylamine Polymer (20) The same operation as in Example 10 was performed except that the arylamine polymer (20) was used instead of the arylamine polymer (15) in Example 10. The phosphorescence spectrum was measured. The triplet level of the arylamine polymer (20) calculated from the obtained phosphorescence spectrum was 2.52 eV.

Example 16 Measurement of Triplet Level of Arylamine Polymer (21) The same operation as in Example 10 was performed except that the arylamine polymer (21) was used instead of the arylamine polymer (15) in Example 10. The phosphorescence spectrum was measured. The triplet level of the arylamine polymer (21) calculated from the obtained phosphorescence spectrum was 2.52 eV.

Example 17 Measurement of Triplet Level of Arylamine Polymer (22) The same operation as in Example 10 was performed except that the arylamine polymer (22) was used instead of the arylamine polymer (15) in Example 10. The phosphorescence spectrum was measured. The triplet level of the arylamine polymer (22) calculated from the obtained phosphorescence spectrum was 2.49 eV.

Example 18 Measurement of Triplet Level of Arylamine Polymer (23) The same operation as in Example 10 was performed except that the arylamine polymer (23) was used instead of the arylamine polymer (15) in Example 10. The phosphorescence spectrum was measured. The triplet level of the arylamine polymer (23) calculated from the obtained phosphorescence spectrum was 2.48 eV.

Comparative Example 1 Measurement of Triplet Level of Arylamine Polymer (100) Poly- (N, N′bis (4-butylphenyl) -N, N′-bis instead of arylamine polymer (15) in Example 10 (Phenyl) benzidine (ADS254BE: manufactured by American Die Source) (100) was used, and the phosphorescence spectrum was measured in the same manner as in Example 10, and was calculated from the obtained phosphorescence spectrum. The triplet level of the arylamine polymer (100) was 2.35 eV.

Example 19 (Production and Evaluation of Device)
The glass substrate on which the ITO transparent electrode (anode) having a thickness of 200 nm was laminated was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Further, ultraviolet ozone cleaning was performed.

  On this substrate, a suspension of poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid (manufactured by Bayer, Baytron P CH8000) was applied by spin coating, and dried at 200 ° C. for 1 hour. As a result, a hole injection layer having a thickness of 80 nm was formed.

  Next, a 0.5 wt% chlorobenzene solution of the arylamine polymer (15) obtained in Example 1 was applied by spin coating and dried at 160 ° C. for 3 hours. As a result, a 20 nm hole transport layer of the arylamine polymer (15) was formed.

Subsequently, after installing in a vacuum evaporation apparatus, it exhausted with the vacuum pump until it became 5x10 <^-4> Pa or less. Subsequently, tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) as a phosphorescent dopant material and 4,4′-bis (N-carbazolyl) biphenyl (CBP) as a host material have a weight ratio of 1:11. Co-deposited at a deposition rate of 0.25 nm / second to obtain a 30 nm emission layer.
Next, BAlq (bis (2-methyl-8-quinolinolato) (p-phenylphenolato) aluminum) was deposited at a deposition rate of 0.3 nm / second to form a 5 nm exciton block layer, and then Alq ₃ (Tris). (8-quinolinolato) aluminum) was deposited at 0.3 nm / second to form a 45 nm electron transport layer. Subsequently, lithium fluoride was deposited as an electron injection layer to a thickness of 0.5 nm at a deposition rate of 0.01 nm / second, and aluminum was further deposited to a thickness of 100 nm at a deposition rate of 0.25 nm / second to form a cathode. In a nitrogen atmosphere, a sealing glass plate was bonded with a UV curable resin to obtain an organic EL element for evaluation.
A current of 20 mA / cm ² was applied to the device thus fabricated, and driving voltage and current efficiency were measured. The results are shown in Table 11.
Example 20 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 19 except that the arylamine polymer (16) synthesized in Example 2 was used instead of the arylamine polymer (15), and the emission characteristics were measured. The results are shown in Table 11.

Example 21 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 19 except that the arylamine polymer (17) synthesized in Example 3 was used instead of the arylamine polymer (15), and the light emission characteristics were measured. The results are shown in Table 11.

Example 22 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 19 except that the arylamine polymer (18) synthesized in Example 4 was used instead of the arylamine polymer (15), and the emission characteristics were measured. The results are shown in Table 11.

Example 23 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 19 except that the arylamine polymer (19) synthesized in Example 5 was used instead of the arylamine polymer (15), and the emission characteristics were measured. The results are shown in Table 11.

Example 24 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 19 except that the arylamine polymer (20) synthesized in Example 6 was used instead of the arylamine polymer (15), and the light emission characteristics were measured. The results are shown in Table 11.

Example 25 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 19 except that the arylamine polymer (21) synthesized in Example 7 was used instead of the arylamine polymer (15), and the emission characteristics were measured. The results are shown in Table 11.

Example 26 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 19 except that the arylamine polymer (22) synthesized in Example 8 was used instead of the arylamine polymer (15), and the emission characteristics were measured. The results are shown in Table 11.

Example 27 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 19 except that the arylamine polymer (23) synthesized in Example 9 was used instead of the arylamine polymer (15), and the light emission characteristics were measured. The results are shown in Table 11.

Comparative Example 2 (device fabrication and evaluation)
In Example 11, instead of the arylamine polymer (15), poly- (N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) benzidine) (ADS254BE: American Die Source) The device was fabricated in the same manner as in Example 11 except that (manufactured) (100) was used, and the emission characteristics were measured. The results are shown in the table.

  In the table, the measurement results of Examples 19 to 27 are shown as relative values obtained by standardizing the measured values of the driving voltage and the luminous efficiency of Comparative Example 2 as 100.

  Therefore, the multibranched arylamine polymer of the present invention can provide a phosphorescent or fluorescent organic EL device having high luminance and low power consumption.

  The arylamine polymer (1a), (1b), (1a ′) or (1b ′) of the present invention has a higher excited triplet level than conventionally known polymer compounds. Therefore, if the arylamine polymer (1a), (1b), (1a ′) or (1b ′) of the present invention is used, an organic electroluminescent device having excellent luminous efficiency and current efficiency can be provided. Therefore, the multibranched arylamine polymer of the present invention can provide a phosphorescent or fluorescent organic EL device having high luminance and low power consumption.

Claims (8)

Following general formula repeating structure represented by (1a) or (1b) will have a backbone that is linked at least two, terminal, each independently, an aromatic group represented by the following general formula (2) A triarylamine polymer , characterized in that it is .

(Where
Ar ¹ and Ar ² are a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms (excluding the m-phenylene group) or a divalent heteroaromatic group having 4 to 20 carbon atoms (these substituents are Each independently, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, and a phenyl having an alkoxy group having 1 to 18 carbon atoms And may have one or more substituents selected from the group consisting of a phenyl group having a dialkylamino group consisting of a group, a halogenated phenyl group, and a C 1-6 alkyl group which may be different) Represents.
Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently 1 selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, and a heteroaromatic group having 4 to 20 carbon atoms. Which may have a substituent of more than one species).
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, carbon The phenyl group which has a dialkylamino group which consists of the phenyl group which has a C1-C18 alkoxy group, or the C1-C6 alkyl group which may differ may be represented.
n represents 0-3.
When n is 2 or 3, Ar ² may be the same or different. )

(In the formula, Ar ⁷ is an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, A C1-C18 alkoxy group, a phenyl group, a phenyl group having a C1-C18 alkyl group, a phenyl group having a C1-C18 alkoxy group, a halogenated phenyl group, and a C1-C6 It may have one or more substituents selected from the group consisting of phenyl groups having dialkylamino groups that may be different alkyl groups). The triarylamine polymer according to claim 1, which is represented by the following general formula (3a) or (3b).

(Where
Ar ¹ and Ar ² are a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms (excluding the m-phenylene group) or a divalent heteroaromatic group having 4 to 20 carbon atoms (these substituents are Each independently, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, and a phenyl having an alkoxy group having 1 to 18 carbon atoms And may have one or more substituents selected from the group consisting of a phenyl group having a dialkylamino group consisting of a group, a halogenated phenyl group, and a C 1-6 alkyl group which may be different) Represents.
Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently 1 selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, and a heteroaromatic group having 4 to 20 carbon atoms. Which may have a substituent of more than one species).
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, carbon The phenyl group which has a dialkylamino group which consists of the phenyl group which has a C1-C18 alkoxy group, or the C1-C6 alkyl group which may differ may be represented.
n represents 0-3.
Ar ⁷ is each independently an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms). Group, a C1-C18 alkoxy group, a phenyl group, a phenyl group having a C1-C18 alkyl group, a phenyl group having a C1-C18 alkoxy group, a halogenated phenyl group, and a C1-C1 6 may have one or more substituents selected from the group consisting of phenyl groups having a dialkylamino group consisting of 6 different alkyl groups.
m represents an integer of 2 or more.
When n is 2 or 3, Ar ² may be the same or different. ) Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently a phenyl group, biphenylyl group, fluorenyl group, carbazolyl group, dibenzothienyl group, dibenzothienylphenyl group, or N-dibenzothienylcarbazolyl group (these substituents are each independently according to any one of claims 1 or claim 2, characterized in that having as a substituent an alkyl group having 1 to 18 carbon atoms is also good.) Arylamine polymer. Ar ¹ and Ar ² are each independently an o-phenylene group, a p-phenylene group, a naphthylene group, a fluorenediyl group, a dibenzofurandiyl group, or a dibenzothiophenediyl group (these substituents are each independently C1-C18 alkyl group, C1-C18 alkoxy group, phenyl group, phenyl group having C1-C18 alkyl group, phenyl group having C1-C18 alkoxy group, phenyl halide And optionally having one or more substituents selected from the group consisting of a phenyl group having a dialkylamino group consisting of a C 1-6 alkyl group which may be different). The arylamine polymer according to any one of claims 1 to 3 . The repeating structure represented by the following general formula (1a) or (1b) has a skeleton in which at least two or more are connected, and the terminal is a secondary amino group, a halogen atom, or both a secondary amino group and a halogen atom. For an arylamine polymer, in the presence of a palladium catalyst and a base, an aryl halide represented by the following general formula (13), an arylamine represented by the following general formula (14), or a general formula (13) method for producing an arylamine polymer according to any one of claims 1 to 4, characterized in that the reaction of both the aryl amine represented by the aryl halide with the general formula (14) to be.

(Where
Ar ¹ and Ar ² are divalent aromatic hydrocarbon groups having 6 to 60 carbon atoms (excluding the m-phenylene group) or divalent heteroaromatic groups having 4 to 20 carbon atoms (these substituents are each Independently, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, and a phenyl group having an alkoxy group having 1 to 18 carbon atoms , A halogenated phenyl group, and optionally having one or more substituents selected from the group consisting of a phenyl group having a dialkylamino group consisting of an optionally substituted alkyl group having 1 to 6 carbon atoms). Represent.
Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently 1 selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, and a heteroaromatic group having 4 to 20 carbon atoms. Which may have a substituent of more than one species).
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a phenyl group having an alkyl group having 1 to 18 carbon atoms, carbon The phenyl group which has a dialkylamino group which consists of the phenyl group which has a C1-C18 alkoxy group, or the C1-C6 alkyl group which may differ may be represented.
n represents 0-3.
When n is 2 or 3, Ar ² may be the same or different. )

Ar ⁷ is an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, 18 alkoxy groups, phenyl groups, phenyl groups having an alkyl group having 1 to 18 carbon atoms, phenyl groups having an alkoxy group having 1 to 18 carbon atoms, halogenated phenyl groups, and different ones having 1 to 6 carbon atoms It may have one or more substituents selected from the group consisting of a phenyl group having a dialkylamino group consisting of a good alkyl group. X ⁶ represents a chlorine atom, a bromine atom, or an iodine atom. )

(In the formula, Ar ⁷ is an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms (these substituents are each independently an alkyl group having 1 to 18 carbon atoms, A C1-C18 alkoxy group, a phenyl group, a phenyl group having a C1-C18 alkyl group, a phenyl group having a C1-C18 alkoxy group, a halogenated phenyl group, and a C1-C6 It may have one or more substituents selected from the group consisting of phenyl groups having dialkylamino groups that may be different alkyl groups). An electronic device comprising the arylamine polymer according to any one of claims 1 to 4 . The electronic device according to claim 6 , wherein the electronic device is an organic EL device. The electronic device according to claim 7 , comprising an arylamine polymer in the light emitting layer, the hole transport layer, or the hole injection layer.

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